含有联苯侧基聚乙炔的合成及其气体渗透性能

檵檵檵檵檵檵檵檵檵檵殝殝殝殝a*aaba116024b910-85051a～1dTaCl5-n-Bu4Sn2a、2b2d。。2a2b。2a2b3a3b。340430℃。2a2bPO2260390barrers3a3bPO273180barrers。O2/N22.4～3.3PO2。。O632A1000-0518201206-0617-06DOI10．3724/SP．J．1095．2012．003132011-07-182011-09-1420101174Tel/[e-mail]/、1-3。1--1-PTMSP4。1--2-4-PTMSDPA400℃PO21500barrers5。6-7。π-π1--2-4-。8desilylation。Scheme1。11．1TaCl599.999%CuI99.5%Ph3P99%ClSiCH3398%ClSiOSiMe395%4--4'-＞96%Aldrichn-Bu4Sn96%PdCl2Ph3P298%Acros-。FT/IR-4100JASCOKBrEX-400JEOLCDCl3PU/SPD-6A/UV-975ShimadzuCHCl3TGA-50Shimadzu296Vol．29Iss．620126CHINESEJOURNALOFAPPLIEDCHEMISTRYJune2012Scheme1Synthesisofsubstitutedpolyacetylenes10℃/minMKSBaratronK-315-NRikaseikiKogyo。1．21--2-4-4'-91-4--2-4-4'-1aN220g64mmol44-100mL。0℃42mL1.58mol/L66mmol1h0℃7.0g64mmolClSiCH3312h。0℃4--4'-。N25.2g17mmol4--4'-、0.25g0.35mmolPdCl2PPh32、0.39g2.1mmolCuI、0.36g1.4mmolPPh3、3.0g17mmol4-100mL5h。200mL。2mol/LHCl。27%1HNMR400MHzCDCl3δ7.80～7.30m12HAr0.30s9HSiCH30.27s9HSiCH313CNMR100MHzCDCl3δ141.0140.8139.9134.0132.0131.6128.5128.3127.0126.3123.3122.290.189.3－1.2－1.0。C26H30Si2/%C77.9878.33H7.867.58。1-4--2-4-4'-1c4--4'-4-1a。71%1HNMR400MHzCDCl3δ7.70～6.8m12HAr1.36s9HCCH313CNMR100MHzCDCl3δ150.8140.9137.4133.4131.9126.8126.6125.8121.6119.4115.8115.689.184.434.631.3。C24H21F/%C87.8487.77H6.746.44。1--2-4--1dN27.8g30mmol1-4--2-250mL0℃19mL1.54mol/L30mmoL2h10g30mmolClSiCH3350mL4h。0℃100mL2mol/LHCl、NaHCO3。20%1HNMR400MHzCDCl3δ7.58～7.43br6HAr7.33br3HAr0.12s27HSiCH313CNMR100MHzCDCl3δ135.9133.7131.6130.6128.3128.2124.2123.290.089.51.8。C23H36O3Si4/%C58.1558.42H7.887.67。816291．3N2。80℃24hcTaCl5=20mmol/Lcn-Bu4Sn=40mmol/L。。1．40.5%～1.0%100μm。24h。8CF3COOHTFAVTFA∶VH2O=9∶124h24h。1．5Dtime-lag1D=l2/6θ1lθ。10～300s。θ10s300s。S2。S=P/D222．1TaCl53TaCl51a～1d1。n-Bu4Sn1a1b1c1--2-4-4'-91cF。TaCl5-n-Bu4Sn1dTaCl5-Et3SiH30%。1TaCl51a～1dTable1Polymerizationofmonomers1a～1dbyTaCl5-basedcatalystaMonomerCocatalystPolymerbYield/%Mw×10－3cMw/Mcn1an-Bu4Sn60873．81bn-Bu4Sn78＞600－1cn-Bu4Sn0－1dn-Bu4Sntrace4．75．71dEt3SiH301．12．21ddEt3SiH602．72．7a．polymerizationintolueneat80℃for24hcM0=0．20mol/LcTaCl5=20mmol/Lcn-Bu4Sn=40mmol/Lb．methanol-insolubleproductc．determinedbyGPCelutedwithCHCl3polystyreneasstandardd．polymerizationindecahydronaphthalenemixtureofcis+trans．2．22a2bTMS3a3b。1TMS2a3aIR3a1250、1120860cm－1TMS8。2a2b700℃SiO223a3bSiO2。2a2b1--2-4-。916612a3aFig．1IRspectraof2aanditsdesilylatedproduct3a2Fig．2TGAcurvesofthepolymersInairheatingrate10℃/min2．3TMS2a、2b2dCHCl3、DMFDMSO3a3b。2a340℃2b、3a3b430℃。10。2．42。3a3bPO22a2b。11。3a3b。O2/N2PO2/PN22.4～3.3PO2“trade-off”。43a3bCO2/CH4Robeson12CO2。microvoidCH4CO2DPCO2/PCH4。111-4-4'--11'--2-PCO2/PCH47.1PCO2440barrersCO2/CH43a3b。2Table2GaspermeabilitycoefficientsPofpolymermembranesPolymerP/barreraHeH2O2N2CO2CH4PO2/PN22a2605402609913002902．62b37081039016022004502．43a1002117322550553．33b2004401806513001702．8a．at25℃intheunitsof1×10－10cm3STPcm/cm2scmHg=1barrer．4CO22a2b3a3bDS。4DS。D3b。3a3b。026293CO2/CH4CO2Fig．3RelationshipbetweentheCO2/CH4permselectivityandCO2permeabilityofthepolymermembranes4CO2Fig．4PlotofSCO2vsDCO2ofthepolymersbeforeandafterdesilylation3TaCl5-n-Bu4Sn80℃Mw87×104。、。1--2-4-。340430℃。PO273～390barrersPO2/PN22.4～3.3PO2。CO2/CH4RobesonCO2。1LiuJLamJWYTangBZ．AcetylenicPolymersSynthesesStructuresandFunctionsJ．ChemRev20091001645-1681．2MasudaT．SubstitutedPolyacetylenesJ．JPolymSciPartAPolymChem200745165-180．3NagaiKMasudaTNakagawaTetal．Poly1-trimethylsilyl-1-propyneandRelatedPolymersSynthesisPropertiesandFunctionsJ．ProgPolymSci200126721-798．4MasudaTIsobeEHigashimuraT．Poly1-trimethylsilyl-1-propyneANewHighPolymerSynthesizedwithTransition-MetalCatalystsandCharacterizedbyExtremelyHighGasPermeabilityJ．JAmChemSoc19831057473-7474．5TsuchiharaKMasudaTHigashimuraT．TractableSilicon-ContainingPolydiphenylacetylenesTheirSynthesisandHighGasPermeabilityJ．JAmChemSoc19911138548-8549．6MichinobuTKumazawaHOtaukiEetal．SynthesisandPropertiesofNitrogen-LinkedPoly27-carbazolesasHole-TransportMaterialforOrganicLightEmittingDiodesJ．JPolymSciPartAPolymChem2009473880-3891．7KimYHKimHSKwonSK．SynthesisandCharacterizationofHighlySolubleandOxygenPermeableNewPolyimidesBasedonTwistedBiphenylDianhydrideandSpirobifluoreneDiamineJ．Macromolecules2005387950-7956．8TeraguchiMMasudaT．PolydiphenylacetyleneMembraneswithHighGasPermeabilityandRemarkableChiralMemoryJ．Macromolecules2002351149-1151．9HuYMShimizuTHattoriKetal．SynthesisandGasPermeationPropertiesofPolydiarylacetylenesHavingSubstitutedandTwistedBiphenylMoietiesJ．JPolymSciPartAPolymChem201048861-868．10LamJWYTangBZ．FunctionalPolyacetylenesJ．AccChemRes200538745-754．11HuYMSandaFMasudaT．SynthesisandPropertiesofVariousPolydiarylacetylenesContainingSiloxyandHydroxyGroupsJ．JPolymSciPartAPolymChem2007454487-4495．12RobesonLM．CorrelationofSeparationFactorVersusPermeabilityforPolymerMembraneJ．JMembrSci199162165-185．1266SynthesisandGasPermeationPropertiesofPolyacetylenesContainingBiphenylPendentGroupsHUYanminga*YUANXuechengaLIZhanshengaMASUDAToshiobaDepartmentofPolymerMaterialsSchoolofChemicalEngineeringDalianUniversityofTechnologyDalian116024ChinabDepartmentofEnvironmentalan